Azo-dyestuffs insoluble in water



lice? AZO-DYESTUFFS INSOLUBLE IN WATER Herbert Kracker, Roland Bamberger, Reinhard Main, and Joachim Ribka, all of Offenbach (Main), Germany, assignors to Farbwerke Hoechst Aktiengesellschatt vormals Meister Lucius & 'Briining, Frankfurt am Main, Germany, a'corporan'on of Germany No Drawing. Filed June 11, 1958, Ser. No. 741,221

Claims priority, application Germany June 15, 1957 6 Claims. (Cl. 260-145) The present invention relates to new azo-dyestufis insoluble in water and to a process for preparing the same; more particularly the invention relates to the complex iron, cobalt, chromium, nickel, copper and manganese compounds of azo-dyestufi's corresponding to the following general formula OO-R wherein Ar represents a radical of the benzene or naphthalene series containing in ortho-positionto the azo group a group capable of forming complex metal compounds, and R represents an alkyl, aryl, cycloalkyl or aralkyl radical, with a diazoor tetrazo-compound of a primary aromatic monoor diamine, the components being free from groups imparting solubility in water.

The process of this invention yields on vegetable fibers and fibers of regenerated cellulose, according to the known dyeing and printing processes, valuable and mainly brown to black dyestufis which are distinguished by good properties of fastness.

Diazoor tetrazo-compounds which can be used in this invention are diazonium or tetrazonium salts, for example diazonium chloride-zinc chloride double salts, diazonium aryl sulfonates or diazonium sulfates, diazoaminoor tetrazoamino compounds or antidiazotates from primary aromatic monoor diamines.

In the present process, coupling components are used the radical Ar of which is free from sulfonic acid groups or such carboxylic acid groups as do not serve for the formation of complex metalcompounds, 'but may .be substituted by a halogen .atom, a nitro, alkyl, sulfonamide or alkylsulfonyl group. These coupling components are disclosed for example in US. patent application Serial No. 727,034, filed on April 8, 1958, in the name of Herbert Kracker, Roland 'Bambe'rger, Reinhard Mohr and Joachim Ribka.

Patented Aug. 23, 1%60 2 The following examples serve to illustrate the invention, but they are not intended to limit it thereto;

Example 1 Cotton fabric is padded on the foulard with the following solution and dried:

20 grams of the complex cobalt compound of the monoazo-dyestufi of the following formula OH OH ll (go-(RH! (obtainable by coupling diazotized l-amino-Z-hydroxy- S-chlorobenzene with 2,4-dihydroxybenzophenone) are pasted up with 20 cc. of sodium hydroxide solution of 38 'B;,

20 grams of Monopol Brilliant oil, and

40 cc. of water, and after the addition of 50 grams of tragacanth :1000 made up to 1 liter with boiling water.

The dried fabric is developed on the foulard with a diazo solution containing, per liter of water, 60 grams of 1- amino-2,5-dichlorobenzene in the form of the diazonium chloride-zinc chloride double salt, and 40 grams of sodium acetate. After an air-passage for 1 minute the material is treated for a short time in water of C., soaped at C. with a solution containing, per liter of Water, 1 gram of a reaction product of about 10 mols of ethylene oxide and '1 mol of isododecyl phenol, and furthermore 3 grams of sodium carbonate, rinsed and dried. A red-brown dyeing of good fastness properties, especially of a very good fastness to light, is obtained. The dyeing process can also be carried out on other fibers, such as viscoseor rayon.

Example 2 60 grams of a mixture (A) containing, in grams, 38.4 grams of the complex cobalt compound of the monoazo-dyestufi from diazotized l-amino-Z-hydroxy-S- chlorobenzene and 2,4-dihydroxy-benzophenone, and furthermore 26 grams of the antidiazotate from l-amino-Z- methoxy-S-chlorobenzene with a content of 52% of the base, are dissolved in 30 grams 20 grams 30 grams 300 grams 500 grams 50 grams 1 kilogram.

Cotton material is printed with the printing paste so obtained. The material is then dried, steamed in an acid medium for 7 minutes, rinsed cold and hot, soaped for 10 minutes with a boiling solution containing, per liter of water, 1 gram of sodium carbonate and 1 gram of a condensation product from an amino alkyl sulfonic acid and a high molecular fatty acid, rinsed again and dried. A reddish brown print is obtained.

When in the above example, the mixture (A) is replaced by a mixture containing, per 100 grams, 38.4 grams of a complex cobalt compound of the monoazodyestufi from diazotized l-amino-Z-hydroxy-S-chlorobenzene and 2,4-dihydroxybenzophenone, and furthermore 25 grams of the autidiazotate from 4,4'-diamino- V 3,3'-dimethoxydiphenyl with a content of 41.5% of the base, a dark brown print is obtained.

Examplej 60 grams of a mixture containing, per 100 grams, 38.4 grams of the complex cobalt compound of the monoazodyestufi from diazotized l-amino-2-hydroxy-5-chlorobenzene; and 2,4-dihydroxy-benzophenone,- and furthermore 27 grams of the diazoamino compound from diazotized l-amino-2-methyl-5-chlorobenzene and l-aminobenzene- "2-carbdxylic acid-S-sulfonic -acid, are dissolved as described in Example-2 and worked upto a printing paste. Cotton fabric is printed with the printing paste so obtained. The materialris then dried, steamed for 7 minutes in an acid medium, and the treatment is completed as described in Example 2. A medium .brown print is obtained.

r Example 7 liCotton'j fabric is padded on the foulard with the following solution and dried:

20 grams of the complex chromium compound of the (obtainable by coupling diazotized l-amino-Z-hydroxy-S-chlorobenzene with 2,4-dihydroxybenzophenone) are pasted up with" 20 cc. of sodium hydroxide solution of 3 8 B.,

20 grams of Monopol Brilliant oil, and

cc. of water, and after the addition of grams of tragacanth :1000 made 'up' with boiling water to 1 liter.

oxide and 1 mol' of isododecyl phenol; and furthermore 3 grams of sodium carbonate, rinsed and dried.

A black-brown dyeing of good'fastness properties is obtained. The dyeing process can also be carried out monoazo-dyestufi of the following formula on other fibers, such as viscose or rayon.

The following table indicates a number of further components which can be used in this invention and also the tints of'the azo-dyestuffs obtainable from these components,'which likewise possess good properties of fast- Coupling component Dlazo component Tint 1 -amino -2 -hydroxy 5 chlorobenzene 1 amino 2 methoxy 5 benzylsulreddish brown.

2,4-dihydroxy-benzophenone, complex cophonylbenzene. i balt compound.

' Do 1-arnlno-5chloro-2-phenoxybenzene Do. 1 amino 2 methoxybenzene 1 5 sul- Do. phonic acid liethylamide. D 1-amino-5-chloro-2-(4'-chloro) -phen- Do.

. oxyhervenc. 7 1 Do 4-amino-3,2'-dlmethyl-l,l-azobenzene dark brown.

1-amino-2-hyrlrory-5-methylbenzene l-aminoauthraquinone full brown. 2,4-dihydroxy-henzophenone, complex cof halt com o nd. 1 amlnn 2 -hydroxy 5 nitrobenzene do red brown.

2,4-dihydroxybenzophenone, com lex cobalt comDo' nd.- V 1 -arnl.no -2 -hydrox v-5-m ethylsulfonylbenzenc l-amino-2-methoxy-5-benzylsulfonyl dark brown.

. 2,4-(1lhydroxybenzophenone, combenzene. 'plex cobalt compo nd. 7 r

1 -arnlno -2 -hvrlrox v 5 chlorobenzene l-eminoanthraqulnone D0. 7 2,4-dinydroxybenzophenone, complex iron com ound. V Do 2 -amino -4 -methoxy 5 -methyl -2'- Do.

' chloro-4-nitro-1,1-a2ohenzene. Do l-amino-2-methyl-4-benzoylamino-5- black brown.

1 -am ino -2 -hydroxy 5 -.chloroben7ene 2,4-(1 ihydroxy-benzophenoue, complex 00- halt compound. 1-amino-2 hydroxy-5-methylbenzene '2,4-dihydroxy-benzophenone, complex iron compound. 7 a 1 amino -2 -hydroxy 5 -chlorobenzene 2,4-dihydroxy-phenylmethylketone,complex coll'salt compound. 0

" 1 amino -2 -hydroxy 5 chlorobenzene 2,4-dihydroxy-ohenylmethylketone, complex 1ron compound,

chlorobenzene. V V 1-ami.uo-2-methoxy-4-mtrobenzene l-amlno-2-methoxy-5-chlorobenzene reddish brown.

medium brown.

1-azobenzene.

reddish, dark brown.

l-amino-2-hydroxy-5-methylbenzene l-aml.uoza.nth1:acpilnone.. reddish brown.

2,4dlhydroxy-phenylmethylketone, complex V ,7 chromium compound r 1-amino-2-methyl-4-benzoylamino-5 D0.

chlorobenzene. 4-amino-3,2-dimethyl-11-azobenzene D0. ydroxy ch -.do red-brown; 2,4-dihydroxy-phenylmethylketone, complex 7 V chromium compound. 7 V

l-amino-2-hydroxy-5-chlorobenzene 1-aminoanthraquinone re lsh rown. 2,4-dlhydroxy-ben zophenone, complex chro- 7 mium compound. 1 a i A ''Do l-ammo-2-methy1-4-benzoylamino-5- D0. chlorobenzene. i

1-amino-2-hydroxy-5-chlorobenzene do D0; hydroxy-benzophenone,complexnickel H V M g 1 compound.

. 1-amino-2-hydroxyfi-methylbenzenev l-aminoanthraquinone medium brown;

ydrioxy-benzophenone,complexnlckel Y I a a compoun r r r l-fi ino-2-hydroxy-51methylbenzene, V4-amino-3,2' dimeth1@ 1,1-azobenzenered-brown 2,4-dihydroxy-benzophenone;complex chr'o -mlum compound. 7"

Coupling component Diazo component Tint 1-amino-2-hydroxy-5-nitrobenzene -.do Do.

2,4-dihydroxy-benzophenone, complex copper compound.

Do 1-am1uo-2-methyl-4-benzoylamlno-5- reddish brown.

chlorobenzene. Do 1-amiuo-2-methoxy-5-benzylsulfonylbrown.

benzene. l-amino-2-hydroxy-5-nitrobenzene do dark brown.

2,4-dihydroxy-benzophenone, complex nickel compound.

Do 1-ernino-2-methyl-4-benzoylamino-5- reddish brown.

chlorobeuzene. Do 4-am1no-3,2-dimethyl-1,1-azobenzene red-brown; 1-amino-2-hydroxy-5-nitrobenzene 1-amino-2-methyl-4-benzoylamino-5- reddish brown.

2,4-dihydroxy-benzophenone, complex chrochlorobenzene. mium compound.

Do 1-%mmo-2-methoxy-5-benzylsuliony1- brown.

enzene. 1-amino-2-hydroxy-s-methyl-sulfonylbenzene 4,4-diam.lno-3,3'-dimethoxydiphenyl Do.

2,4-dihydroxy-benzophenone, complex nickel compound.

We claim: 1. The complex metal compounds 4. The complex cobalt compound of the azo-dyestufi selected from the group consisting of iron, cobalt, chromium, nickel, copper and manganese compounds of azo-dyestuifs corresponding to the following general formula wherein R represents a member selected from the group consisting of lower alkyl and phenyl, R represents a corresponding to the following formula ()3 I011 CIJCH:

N=N N=NO 0 cm 01 0-C4H5 2 n 5. The complex cobalt compound of the azo-dyestufi member selected from the group consisting of radicals of the benzene, diphenyl and anthraqui none series, X represents a member selected from the group consisting of chlorine, nitro, methyl and methylsulfonyl, and n stands for one of the numbers 1 and 2.

2. The complex cobalt compound of the azo-dyestuif corresponding to the following formula Ci H (Ill OH l 3. The complex cobalt compound of the azo-dyestuif corresponding to the following formula C O-GsHs corresponding to the following formula CO-OsHl 6. The complex cobalt compound of the azo-dyestufE corresponding to the following formula on on com N=N N0z References Cited in the file of this patent UNITED STATES PATENTS Dahlen Sept. 21, 1937 Rossander et a]. Oct. 3, 1939 

1. THE COMPLEX METAL COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF IRON, COBALT, CHROMIUM, NICKEL, COPPER AND MANGANESE COMPOUNDS OF AZO-DYESTUFFS CORRESPONDING TO THE FOLLOWING GENERAL FORMULA 